CN110327882A - The preparation method and application of multidigit activation and modified reed-south reed charcoal - Google Patents
The preparation method and application of multidigit activation and modified reed-south reed charcoal Download PDFInfo
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- CN110327882A CN110327882A CN201910622757.7A CN201910622757A CN110327882A CN 110327882 A CN110327882 A CN 110327882A CN 201910622757 A CN201910622757 A CN 201910622757A CN 110327882 A CN110327882 A CN 110327882A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/007—Reclamation of contaminated soil by removing contaminants floating on the water table
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4843—Algae, aquatic plants or sea vegetals, e.g. seeweeds, eelgrass
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention relates to water bodys and heavy metal in soil to pollute process field, specially a kind of multidigit activation and the application of modified reed-south reed charcoal preparation method and its removal heavy metal zinc, cadmium.Preparation method includes first cleaning reed-south reed biomass, drying, crushing, the charcoal of unactivated modification is made after being sufficiently stirred by ultrasonic in manganite powder solution through low-temperature hydrothermal carbonization, charcoal is impregnated in calcium chloride-hydrogen peroxide solution again, charcoal-calcium chloride-hydrogen peroxide solution is activated by microwave, it is again that the charcoal after drying is modified by ultraviolet radioactive, the charcoal of activation modification is obtained, obtained charcoal is used for the removal of water body and heavy metal in soil zinc and cadmium.Application method includes the following: that the charcoal of activation modification is added to heavy metal zinc, carries out adsorption reaction in cadmium waste water；Or be added directly into heavy metal zinc, in cadmium pollution soil, mix well, after aging for a period of time, complete to heavy metal-polluted soil zinc, cadmium pollution it is biological prosthetic.
Description
Technical field
The present invention relates to water body and heavy metal in soil to pollute process field, and in particular to a kind of multidigit activation and modified
Reed-south reed charcoal preparation method and its application for removing heavy metal zinc, cadmium.
Background technique
Subtropical monsoon climate at Jiangxi, soil belong to red soil, and red soil itself has development degree height and eluviation strong
Strong feature, along with the unreasonable development to red soil resources, red soil acidification phenomenon is commonplace, while by Poyang Lake
The mining of five river valley of upstream, smelting, the influence of Industrial " three Waste ", some areas agricultural land soil and farmland irrigating water's huge sum of money
It is more serious to belong to damage ratio, especially heavy metal zinc, cadmium pollution.Since zinc, cadmium can be enriched in vivo, entered by food chain
Human body causes slow poisoning, the exceeded big problem for having become Jiangxi grain security of rice zinc, cadmium.
Poyang Lake in Jiangxi province region wetland plant is resourceful, and wherein reed-south reed biomass biomass Poyang Lake is always biological
30% or more of amount, wetland reed-south reed biomass constituent are mostly cellulose, hemicellulose, lignin etc., are contained big
Measure hydroxyl, carboxyl, carbonic acyl radical isoreactivity group；Basic framework is made of carbon, using reed-south reed biomass as raw material
Prepare charcoal adsorbent material, charcoal pH with higher applies and easily forms heavy metal precipitation in the soil, can play pair
The absorption passivation of heavy metal.
Charcoal mainly passes through the heavy metal in five kinds of effect absorption passivation soil, including adsorption, surface are complexed, are heavy
Shallow lake effect, ion exchange and electrostatic interaction, wherein it adsorbs the effect for fixing heavy metal are as follows: precipitation > complexing > is quiet
Electro ultrafiltration, ion exchange > physical absorption.However charcoal is limited to the absorption passivation ability of heavy metal contaminants, passes through physics
Method and chemical method are modified to charcoal progress performance to promote its important link for adsorbing passivation ability.Pass through peroxidating
The chemical oxidation of hydrogen acts on, and the oxygen-containing functional group of biological carbon surface can be improved, and improves the adsorption capacity to heavy metal.In addition,
Microwave heating activation can directly provide heating to charcoal inside, obtain different pore structures and specific surface area, have letter
Single easy advantage.The modified surface texture that can change charcoal of charcoal clearance superchlorination calcium, so that biological carbon surface object
Reason suction-operated is changed into ion exchange, has more stable adsorption effect.Two methods (chemical activation is used simultaneously
Activated with microwave) heavy metal zinc of biological carbon surface, the quantity and charcoal of cadmium adsorption site and functional group are increased with this
Surface area changes part suction type, can be improved its absorption crystallized ability and stability to heavy metal zinc, cadmium.Patent Shen
Please 109401755 A of number CN disclose a kind of straw biological charcoal method of modifying for heavy-metal contaminated soil reparation, use
30% sodium hydroxide is modified, has relatively good repairing effect to Available zinc, cadmium；108940203 A of number of patent application CN is public
A kind of Three Gorges adaptability vegetation charcoal preparation method and applications of cloth, using NaOH after charcoal processing and H2O2Combined modified method,
To NH4+-N ion has stronger adsorption capacity, and there is no verified for heavy metal.109110863 A of application number CN is public
The method of cloth fortimicin in chemical activation/micro-wave digestion activation biological carbon materials removal water body, also mainly for organic
Pollution, is not directed to heavy metal pollution field.
Summary of the invention
To solve the above problems, the present invention provides a kind of multidigit activation and modified reed-south reed charcoal preparation side
Method and its application.Specific technical solution is as follows:
A kind of multidigit activation and modified reed-south reed charcoal preparation method: the following steps are included:
(1) first reed-south reed biomass washing, dry, crushing are added in manganite powder solution and are submerged, through sufficiently ultrasound
It stirs and evenly mixs, low-temperature hydrothermal, which is carbonized, is made the charcoal of unactivated modification；
(2) charcoal that step (1) obtains is subjected to microwave activation in calcium chloride-hydrogen peroxide solution；
(3) it is modified to get the charcoal for arriving activation modification to carry out ultraviolet radioactive for the charcoal for obtaining step (2).
Further, reed, southern reed biomass mass ratio are 3:2 in step (1), are crushed to 1-2cm quarter butt, manganite powder
It sieves with 100 mesh sieve, additional amount 200g/L；Hydrothermal carbonization temperature is 180 DEG C in low-temperature hydrothermal carbonisation, and the hydrothermal carbonization time is
15h。
Further, the step (2) includes
(2.1) charcoal that step (1) obtains is added in calcium chloride-hydrogen peroxide solution first and is impregnated, soaking time
For for 24 hours；
(2.2) charcoal-calcium chloride-hydrogen peroxide mixture of above-mentioned steps (2.1) is placed in Hyperfrequency waves eliminating stove, is carried out
Microwave activation, charcoal washing, drying after microwave activation.
Further, the step (3) is that the charcoal of above-mentioned steps (2) produced is placed in ultraviolet radioactive chamber
In, it carries out ultraviolet radioactive and is modified, finally obtain the charcoal of activation modification.
Further, the charcoal that every liter of calcium chloride-hydrogen peroxide solution is launched is 100 grams, the calcium chloride-peroxide
Changing calcium chloride mass concentration in hydrogen mixed liquor is 50g/L, and hydrogen peroxide mass concentration is 500g/L, concentration of hydrogen peroxide 30%.
Further, the microwave power is set as 2 watts of every milliliter of mixed liquor, and microwave activation time is 30min；
Further, the ultraviolet irradiation uses the ultraviolet lamp of 254nm wavelength, and UV radiation intensity is 500 μ W/cm2,
Irradiation time is 36 h.
Further, a kind of application using charcoal prepared by aforementioned preparation process, by preparation-obtained biology
Removal of the charcoal for water body and heavy metal in soil zinc and cadmium.
Further, minimizing technology is the following steps are included: be added to heavy metal zinc, cadmium waste water for the charcoal of activation modification
In, after adsorption reaction for a period of time, the charcoal after absorption is collected by filtering or precipitation and separation；Or charcoal is added to weight
It in metallic zinc, cadmium pollution soil, mixes well, for a period of time, the biology of heavy metal-polluted soil zinc, cadmium pollution is repaired in completion for aging
It is multiple.
Further, in 200-2000 PPM, 5.0-100.0PPM, pH control exists for the concentration control of the zinc in water body, cadmium
2.0-10.0 temperature is controlled at 25 DEG C.
Further, ZINC IN SOIL concentration is between 300-2000 PPM, and cadmium concentration is between 0.2-12 PPM.
The utility model has the advantages that
Cellulose, the hemicellulose level of reed and Nan Di that the present invention chooses are relatively high, and charcoal is made with higher in pyrolysis
PH, be applied in soil or water body and easily form heavy metal precipitation, can be improved its to heavy metal zinc, cadmium passivation effect it is steady
It is qualitative.
The charcoal that the present invention uses is produced mode and is carbonized using 180 degrees Celsius of low-temperature hydrothermals, and nano particle is bright in product
Aobvious, the morphology of the aggregate formed by nano particle and nano-plates is presented in marshalling between nanoparticle, the charcoal tool produced
Have the advantages that surface functional group is abundant, preferably plays the suction-operated to heavy metal zinc, cadmium.
Manganite is added in the present invention during hydrothermal carbonization, and manganite has stronger absorption and oxidability, can
It is attached to biological carbon surface, improves the adsorption capacity to heavy metal；Manganite itself is in alkalinity, and being attached to biological carbon surface can be with
The pH value of charcoal itself is improved, the precipitation to heavy metal is improved.
The method of modifying that the present invention uses is physics and chemical modification.First calcium chloride and peroxide will be dipped into raw material
Change in hydrogen mixed liquor, calcium chloride modification can make charcoal surface texture generation table change, the calcium of charcoal area load from
With the heavy metal ion in water and in soil ion exchange occurs for son, stronger to the stability of heavy metal adsorption；Oxidation
Agent modification can introduce oxygen atom in biological carbon surface, and oxygen content increases so that biological carbon surface is easier to generate more carboxyls etc. and contain
Oxygen functional group.
React activated carbon surface functional group sufficiently with modifying agent by microwave activation after being chemically modified, so that reed-
The aromatization degree of the dehydration of the biomass-based charcoal of Nan Di and decarboxylic reaction, charcoal is improved, and can enhance biology
Charcoal is to heavy metal zinc, cadmium surfaces suction-operated；Finally by ultraviolet radioactive biological carbon materials, oxygen-containing group number can be significantly improved
Charcoal can be enhanced to the complexing of heavy metal zinc, cadmium in amount.
The present invention is using wetland plant reed-south reed biomass as raw material, and from a wealth of sources, low production cost realizes
The comprehensive utilization of resource；And it is multi-faceted charcoal is modified and is activated so that the absorption property of charcoal greatly improves, ring
Border is friendly, is suitble to the removal to natural ecological environment water body or heavy metal in soil.
Detailed description of the invention
Fig. 1 the method for the present invention general flow chart.
Specific embodiment
The present invention is described in further details below with reference to specific embodiment
Embodiment 1
Embodiment is compared with the reed-south reed biomass charcoal for not carrying out activation modification, and analyzing activated modification biological charcoal is to molten
The absorption of zinc, cadmium in liquid.
Charcoal forming steps are as follows:
1) it will be added in manganite powder solution and submerge after leaching reed-south reed biomass washing drying and crushing, stirred through abundant ultrasound
Mixing is mixed, low-temperature hydrothermal carbonization is carried out, hydrothermal carbonization temperature is 180 degrees Celsius, and the hydrothermal carbonization time is 15 hours, is made and does not live
Change modified charcoal；
2) 100 grams of the charcoal of unactivated modification are added in 1 liter of calcium chloride-hydrogen peroxide solution and are impregnated, sufficiently reacted
24 hours；Calcium chloride-hydrogen peroxide solution is added to the preparation method is as follows: take 500ml pure water, 500ml hydrogen peroxide
In container, 50 grams of calcium chloride are then added, sufficiently ultrasonic agitation mixes, and temperature is controlled in room temperature condition；
3) the charcoal mixed liquor that step (2) obtains is placed in counteracting tank, carries out microwave activation, cooling, the microwave power
2 watts of every milliliter of mixed liquor are set as, microwave activation time is 30min；It is thoroughly washed to repeatedly filtering with deionized water again,
75 DEG C of drying, obtain the charcoal of microwave activation modification；
4) charcoal of above-mentioned steps (3) produced is placed in ultraviolet radioactive chamber, the ultraviolet radiation lamp of 254nm wavelength
Irradiation, the light intensity of affiliated ultraviolet radioactive are 500 μ W/cm2, and irradiation time is 36 h, carry out ultraviolet radioactive and are modified, obtain most
Whole activation modification charcoal.
Unactivated modification biological charcoal and activation modification charcoal are added to zinc, in cadmium mixed liquor according to 10mg/L, configuration
The mixed solution that zinc concentration is 1000PPM, cadmium concentration is 10PPM.Adsorption reaction for 24 hours, measures zinc, cadmium concentration in liquid, obtains
Unactivated modification biological charcoal is 74.8%, 82.1% to the adsorption rate of zinc, cadmium, and charcoal is to zinc in solution, cadmium after activation modification
Adsorption rate is 85.2%, 97.7%, and charcoal adsorption rate improves 10.4 and 15.6 percentage points after activation modification.
Embodiment 2
Compared with the reed-south reed biomass charcoal for not carrying out activation modification, analyzing activated modification biological charcoal is to Jiangxi Guixi
The absorption of characteristic of acid red soil soil available zinc, cadmium, charcoal forming steps are same as Example 1.
Zinc, the cadmium that unactivated modification biological charcoal and activation modification charcoal are added to Jiangxi Guixi according to 1% mass ratio are dirty
(soil pH value 4.83, the total cadmium of soil are 2.53PPM, and total zinc is 80.81PPM) is contaminated in soil, is mixed well, natural aging 4
After a month, the biological prosthetic of the heavy metal pollution to soil is completed.Using the CaCl of 0 .01moL2Solution extracts in soil effectively
Then state Cd measures its concentration using graphite furnace atomic absorption spectrophotometer, as a result such as table 1(cadmium), table 2(zinc) shown in.
Charcoal aging front and back soil available Cd and repair rate are added in 1 Jiangxi Guixi characteristic of acid red soil of table
| Before aging | After aging | Repair rate | |
| Unactivated modification biological charcoal | 0.379±0.015 | 0.207±0.010 | 45.3% |
| Activation modification charcoal | 0.380±0.012 | 0.151±0.008 | 61.2% |
Charcoal aging front and back soil available zinc and repair rate are added in 2 Jiangxi Guixi characteristic of acid red soil of table
| Before aging | After aging | Repair rate | |
| Unactivated modification biological charcoal | 10.023±0.021 | 1.663±0.013 | 83.4% |
| Activation modification charcoal | 10.018±0.019 | 0.441±0.009 | 95.6% |
Embodiment 3
Compared with the reed-south reed biomass charcoal for not carrying out activation modification, analyzing activated modification biological charcoal is to Guangdong Renhua
The absorption of soil available zinc, cadmium, charcoal forming steps are same as Example 1.
The zinc cadmium that unactivated modification biological charcoal and activation modification charcoal are added to Guangdong Renhua according to 1% mass ratio is dirty
(soil pH value 5.52, the total cadmium of soil are 3.93PPM, and total zinc is 1160.37PPM) is contaminated in soil, is mixed well, natural aging
After 4 months, the biological prosthetic of the heavy metal pollution to soil is completed.Using the CaCl of 0 .01moL2Have in solution extraction soil
Imitate state Cd, its concentration then measured using graphite furnace atomic absorption spectrophotometer, as a result such as table 3(cadmium), table 4(zinc) shown in:
Charcoal aging front and back soil available Cd and repair rate are added in 3 Guangdong Renhua soil of table
| Before aging | After aging | Repair rate | |
| Unactivated modification biological charcoal | 0.442±0.011 | 0.220±0.011 | 50.3% |
| Activation modification charcoal | 0.441±0.015 | 0.175±0.010 | 60.4% |
Charcoal aging front and back soil available zinc and repair rate are added in 4 Guangdong Renhua soil of table
| Before aging | After aging | Repair rate | |
| Unactivated modification biological charcoal | 208.86±0.014 | 73.518±0.017 | 64.8% |
| Activation modification charcoal | 208.82±0.024 | 47.611±0.020 | 78.2% |
Embodiment 4
Adsorption analysis of the activation modification charcoal to soil extract zinc, cadmium.
Charcoal forming steps are same as Example 1.
The charcoal of activation modification is added to according to 0.2% mass ratio and uniformly applies the paddy field soil for arriving yueyang, hunan
In (soil pH value 6.88, total cadmium are 1.94PPM, and total zinc is 926.14PPM) in pedotheque, keeping soil moisture is maximum
Field capacity surveys the content of zinc, cadmium in leachate in soil after reaction 24 hours.The results show that cadmium is in soil extract
0.0032mg/L, lower than the prohibitive content of 0.005mg/L in " agricultural irrigation water quality standard " (GB5084-2005).
Comparative example 1
Ultraviolet radioactive modification is understood for comparison and adsorbs heavy metal-passivated influence to charcoal, this comparative example will pass through ultraviolet radioactive
The modified comparative study that absorption heavy metal zinc, cadmium are carried out with charcoal that is being modified without ultraviolet radioactive, the forming steps of charcoal
With embodiment 1, except that whether passing through 254nm wavelength by the charcoal that step (3) are produced, radiation intensity is 500 μ
W/cm2, ultraviolet radioactive that irradiation time is 36 h it is modified.
Zinc, cadmium will be added to according to 10mg/L without the modified charcoal of the modified charcoal of ultraviolet radioactive and ultraviolet radioactive
In mixed liquor, configuration zinc concentration is 1000PPM, and cadmium concentration is the mixed solution of 10PPM.Adsorption reaction for 24 hours, measures in liquid
Zinc, cadmium concentration, the modified charcoal of discovery ultraviolet radioactive is compared with without the modified charcoal of ultraviolet radioactive, to weight in water body
Metallic zinc, the adsorption rate of cadmium improve 3.1%, 5.7%.
The preferred embodiment of the patent is described in detail above, but this patent is not limited to above-mentioned embodiment party
Formula within the knowledge of one of ordinary skill in the art can also be under the premise of not departing from this patent objective
Various changes can be made.
Claims (10)
1. the preparation method of a kind of multidigit activation and modified reed-south reed charcoal: characterized by comprising the following steps:
First by reed-south reed biomass washing, dry, crushing, it is added in manganite powder solution and submerges, be sufficiently stirred by ultrasonic
It mixes, low-temperature hydrothermal, which is carbonized, is made the charcoal of unactivated modification；
The charcoal that step (1) is obtained microwave in calcium chloride-hydrogen peroxide solution activates；
It is modified to get the charcoal for arriving activation modification that the charcoal that step (2) are obtained carries out ultraviolet radioactive.
2. preparation method according to claim 1, it is characterised in that: reed, southern reed biomass mass ratio are in step (1)
3:2 is crushed to 1-2cm quarter butt, and manganite powder sieves with 100 mesh sieve, additional amount 200g/L；Hydrothermal carbonization temperature during hydrothermal carbonization
Degree is 180 DEG C, and the hydrothermal carbonization time is 15h.
3. preparation method according to claim 1, it is characterised in that: the step (2) includes:
(2.1) charcoal that step (1) obtains is added in calcium chloride-hydrogen peroxide solution first and is impregnated, soaking time
For for 24 hours；
(2.2) charcoal-calcium chloride of above-mentioned steps (2.1)-hydrogen peroxide mixture is subjected to microwave activation, after microwave activation
By charcoal washing, drying.
4. preparation method according to claim 3, it is characterised in that: in the step (2.1), every liter of calcium chloride-peroxide
Changing the charcoal that hydrogen mixed liquor is launched is 100g, and calcium chloride mass concentration is 50g/ in the calcium chloride-hydrogen peroxide solution
L, hydrogen peroxide mass concentration are 500g/L, concentration of hydrogen peroxide 30%.
5. preparation method according to claim 3, it is characterised in that: the power of the activation of microwave described in step (2.2) is set
2 watts of every milliliter of mixed liquor are set to, microwave activation time is 30min.
6. preparation method according to claim 1, it is characterised in that: in the step (3), the ultraviolet irradiation is used
The ultraviolet lamp of 254nm wavelength, UV radiation intensity are 500 μ W/cm2, irradiation time is 36 h.
7. a kind of application using charcoal prepared by any preparation method of claim 1-6, it is characterised in that: will make
Removal of the charcoal of standby activation modification for water body or heavy metal in soil zinc and cadmium.
8. application according to claim 7, it is characterised in that: minimizing technology is the following steps are included: by after activation modification
Charcoal is added to containing in heavy metal zinc, cadmium waste water, after adsorption reaction for a period of time, is collected and is inhaled by filtering or precipitation and separation
Attached charcoal completes the processing to Heavy Metals in Waters zinc, cadmium；Or charcoal is added to dirty containing heavy metal zinc, cadmium
Contaminate soil in, mix well, aging for a period of time, complete to heavy metal-polluted soil zinc, cadmium pollution it is biological prosthetic.
9. application according to claim 7, it is characterised in that: the concentration of zinc, cadmium in water body is controlled in 200-2000
PPM, 5.0-100.0PPM, pH control are controlled in 2.0-10.0, temperature at 25 DEG C.
10. application according to claim 7, it is characterised in that: for ZINC IN SOIL concentration between 300-2000 PPM, cadmium is dense
Degree is between 0.2-12 PPM.
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| CN111778031A (en) * | 2020-06-23 | 2020-10-16 | 北京建工环境修复股份有限公司 | Soil remediation agent and preparation method and application thereof |
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| CN115518617A (en) * | 2022-10-24 | 2022-12-27 | 沈阳理工大学 | Preparation method of low C/N sewage dephosphorization and denitrification material |
| CN115608318A (en) * | 2022-09-21 | 2023-01-17 | 江苏省生态环境评估中心（江苏省排污权登记与交易管理中心） | Reed biochar material synthesized by phosphoric acid activation modification |
| CN116328731A (en) * | 2023-04-19 | 2023-06-27 | 西北农林科技大学 | Preparation method of sulfur-calcium loaded biochar material |
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